WO2019033189A1

WO2019033189A1 - Coolant composition, use of said composition, cooling apparatus, packaged product and packaging process

Info

Publication number: WO2019033189A1
Application number: PCT/BR2018/050283
Authority: WO
Inventors: Flávio Azzi Pacheco BORBA
Original assignee: Ideal Eficiência Energética Ltda.
Priority date: 2017-08-16
Filing date: 2018-08-09
Publication date: 2019-02-21
Also published as: US20200231853A1; BR102017017568B1; BR102017017568A2

Abstract

The present invention relates to a coolant composition comprising the following components: a) at least one difluoromethane; b) at least one pentafluoroethane; c) at least one tetrafluoroethane; d) at least one tetrafluoropropene; and e) at least one trifluoroethane. The composition preferably also comprises nanoparticles selected from the group consisting of: graphite, silver, zinc and silicon dioxide, and mixtures thereof.

Description

COMPOSITION OF REFRIGERANT FLUID, USE OF COMPOSITION, REFRIGERATOR, PACKAGED PRODUCT AND PROCESS OF

PACKAGING

FIELD OF THE INVENTION

The present invention relates to a refrigerant composition comprising a mixture of specific components as well as their use in refrigerating appliances.

BACKGROUND OF THE INVENTION

Numerous refrigerant compositions are known in the art, which usually comprise mixtures of refrigerant gases, applied to refrigeration appliances.

The choice of specific components of these refrigerant gas mixtures may involve a number of technical factors, generally aligned in order to optimize the energy expenditure and environmental impact of the refrigeration apparatus itself.

Cooling systems are responsible for much of the world's electrical energy expenditure, so any and all modifications in refrigerants will positively impact the energy expenditure of the system as a whole. is highly desirable.

It is also desirable that the refrigerant fluids have low global warming potential (GWP). a widely used parameter for selecting refrigerant gases for commercial blends, and explaining the shift from traditional CFCs and HCFCs to currently used hydrofluorocarbons (HFCs) or hydrofluorolefins (HFOs).

In this regard, US 8038899 describes refrigerant compositions comprising mixtures of HFCs with siloxane solubilizing agents, in an attempt to improve the miscibility of the blend provided. The mixtures disclosed herein comprise up to three refrigerant gases.

Further, US Pat. No. 9540554 discloses three or four component refrigerant mixtures HFCs and hydrofluorolefins (HFOs) in order to replace blends of the prior art which have high GWP values and which can be used in various systems and apparatus of cooling.

Likewise, US 9359540 discloses compositions of refrigerants containing up to three components, likewise seeking mixtures which have lower GWP values and better energy performance.

Thus, according to the above information, it is noted that the current state of the art follows in pursuit of refrigerant compositions whose mixtures of specific components are capable of promoting an energetic gain to the refrigerating apparatus, and having low GWP values.

SUMMARY OF THE INVENTION

In a first aspect, the present invention relates to a refrigerant composition comprising the following components:

a) at least one difluoromethane;

b) at least one pentafluorethane;

c) at least one tetrafluoroethane;

d) at least one tetrafluoropropene;

e) at least one trifluoroethane.

In a preferred embodiment, the tetrafluoroethane is 1,1,1,2-tetrafluoroethane.

In another preferred embodiment, the tetrafluoropropene is 2,3,3,3-tetrafluoropropene.

In another preferred embodiment, the trifluoroethane is 1,1,1-trifluoroethane.

In another preferred embodiment the components of the refrigerant composition have the following proportions:

a) from 20 to 30% by weight of difluoromethane, based on the total weight of the composition;

b) from 20 to 30% by weight of pentafluoroethane, based on the total weight of the composition;

c) from 15 to 25% by weight of tetrafluoroethane. in relation to the total weight of the composition;

d) from 15 to 25% by weight of tetrafluoropropene, relative to the total weight of the composition;

e) from 5 to 15% by weight of trifluoroethane, based on the total weight of the composition.

In another preferred embodiment, the refrigerant composition further comprises nanoparticles, which preferably have a particle size ranging from 1 to 20 nm. In another preferred embodiment, the nanoparticles are selected from the group consisting of: graphite, silver, zinc and silicon dioxide, and mixtures thereof, preferably silicon dioxide.

In another preferred embodiment, the amount of nanoparticles is up to 5% by weight, based on the total weight of the composition.

The present invention also relates to the use of the composition, as defined above, in a refrigerator apparatus.

Another object of the present invention is a refrigeration apparatus comprising at least one heat exchanger, at least one compressor, and the refrigerant composition as defined above.

A further object of the present invention is a packaged product comprising an outer wrapper, which stores the refrigerant composition, as defined above.

Finally, another object of the present invention is a process for packaging the refrigerant composition, as defined above, comprising the steps of:

a) transferring the components a) to e) in the liquid phase to a watertight system;

b) weighing the composition; and

c) envaze of the composition.

Figures 1 to 7 show power plots consumed by refrigerating appliances utilizing the refrigerant composition of the present invention compared to other compositions of the prior art.

Figure 8 shows an energy and current consumption chart for refrigeration appliances utilizing the refrigerant composition according to the present invention, as compared to other compositions of the prior art.

Figure 9 shows a graph of variation of blowing temperature and external air for refrigerating appliances using the refrigerant composition according to the present invention, as compared to other compositions of the prior art.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a refrigerant composition which comprises a mixture of five components, described below:

a) at least one difluoromethane;

b) at least one pentafluorethane;

c) at least one tetrafluoroethane;

d) at least one tetrafluoropropene; and

e) at least one trifluoroethane.

For difluoromethane, there is only one possible configuration of the fluorine atoms, detailed below in Formula (I):

(I).

Difluoromethane is a known refrigerant known from the state of the art, marketed as "R32a", and CAS number: 75-10-5.

Likewise, for pentafluoroethane, there is also only one possible configuration of the fluorine atoms, detailed below in Formula (II):

(II) -

Pentafluoroethane is a refrigerant known from the prior art, marketed as "R125a", and CAS No .: 354-33-6.

As for tetrafluoroethane, more than one configuration is possible, with 1,1,1,2-tetrafluoroethane being preferred, detailed below in formula (III):

(III).

Tetrafluoroethane is a refrigerant known from the prior art, marketed as "R134a". and CAS number: 81-197-2.

Tetrafluoropropene also has more than one possible configuration, 2,3,3,3-tetrafluoropropene being preferred. the structure of which is detailed below in Formula (IV):

(IV).

Tetrafluoropropene is a refrigerant known from the prior art, traded by reference "HF01234yf", and CAS number: 754-1 2-1.

Finally, the preferred trifluoroethane is 1,1,1-trifluoroethane, the structure of which is detailed in Formula (V) below:

Trifluoroethane is a refrigerant known from the prior art, marketed as "R143a", and CAS No: 420-46-2.

All five components of the blend should be present so that the best energy performance and the lowest GWP values are obtained, in accordance with the present invention.

Preferably, the components of the refrigerant composition are present in the following proportions:

d) from 15 to 25%. by weight of tetrafluoropropene, relative to the total weight of the composition;

It is important to note that the ratio of the components of the present invention is not readily derived from the state of the art. In particular, the The concentration of 15 to 25% of tetrafluoroethane escapes from the commonly used one, since this component is usually used in the ratio of base, ie in higher concentrations.

The choice of each of the five components of the composition of the present invention also involved extensive planning. The presence of trifluoroethane, for example, implies an optimization of the giide value, which refers to the variation between the superheating and supercooling temperatures.

The refrigerant compositions of the present invention have ozone depletion potential (ODP) equal to zero, and low GWP values in relation to compositions known in the art.

The refrigerant fluid compositions of the present invention have lower working pressure, which generates an expressive and energetic thermal gain, creating relief to the refrigeration system as a whole.

In addition, the refrigerant fluid compositions of the present invention may be used with any type of lubricating oil, increasing their versatility and allowing their application in different refrigeration appliances.

In particular, the compositions of the present invention may be applied in the area of refrigeration, air conditioning, and heating with heat exchangers. More specifically, it is possible to implement air conditioners in all models, automotive air-conditioning, refrigerators, cold rooms, refrigerated counters, refrigerated and refrigerated equipment of all kinds, pool heaters, heaters in general with fluid heat.

The refrigerant composition of the present invention provides an energetic efficiency gain to the refrigerating appliances.

In a preferred embodiment, the refrigerant composition further comprises nanoparticles, which preferably have a particle size ranging from 1 to 20 nm.

The nanoparticles are preferably dispersed in the mixture of the refrigerant base fluid, acting to decrease the friction of the tubing surface of the refrigeration apparatus and the compressor. In this way, it is possible to decrease the oil temperature and, especially, the compressor sump temperature, providing gain of efficiency and gain with the reduction in the energy consumption of the refrigeration appliance, as a consequence of the increase in thermodynamic performance as a whole.

Still, ordinary coolant fluids do not have lubricating properties, bringing greater wear to refrigerators and compressors, with excessive wear of the equipment as a whole, which decreases its service life.

Thus, the presence of the nanoparticles in the refrigerant composition of the present invention provides significant savings in the total consumption of electric power and power consumed by the refrigerating apparatus. with increased performance and thermal efficiency of the implemented equipment. Furthermore, it extends the life of the lubricating oil and, consequently, the compressor of the refrigerating appliance.

As noted above, the nanoparticles provide a considerable reduction in the friction caused by the grooves of the tubing of the refrigerator apparatus. The nanoparticles fill in said grooves, practically reducing the coefficient of friction between the refrigerant and the refrigerant piping surface, as well as on the compressor head itself, forming a protective film with a consequent increase of lubrication. This decreases the working temperature of the refrigerator and improves the energy efficiency of the equipment as a whole.

The presence of the nanoparticles also causes an increase in the thermal conductivity of the refrigerant, boosting the temperature gain by reaching the set point more quickly and efficiently, generating gains and reducing the consumption of refrigerating appliances, on average, by 30%. economy.

Since the refrigerant composition of the present invention comprises a mixture of refrigerant gases, the nanoparticles play another important role in the stability of the composition, so that the mixtures do not separate into several phases.

Preferably, the nanoparticles are selected from the group consisting of: graphite, silver, zinc and silicon dioxide, and mixtures thereof, more preferably silicon dioxide.

In a preferred embodiment, the nanoparticles are present in small amounts, particularly up to 5% by weight. in relation to weight total composition. In a preferred embodiment, the amount of nanoparticles ranges from 0.1 to 5% by weight.

The present invention also relates to the use of the composition, as defined above, in a refrigerating apparatus, as well as to a refrigerating apparatus itself, comprising at least one heat exchanger, at least one compressor, and the refrigerant composition according to the invention. defined above.

As highlighted above, by refrigeration appliance is meant air-conditioning equipment of all models, automotive air-conditioning, refrigerators, cold rooms, refrigerated counters, refrigerated and refrigerated equipment of all kinds, pool heaters, general fluid heaters heat exchangers

Yet another object of the present invention is a packaged product comprising an outer wrapper, which stores the refrigerant composition as defined above.

The refrigerant composition can be packaged via liquid transfer in a sealed system via the vacuum pump and suction, weighing and packaging compressors of the composition. In a particularly preferred embodiment, the refrigerant composition is packed together with the nanoparticles, allowing their easy application to different refrigerating appliances.

Examples

Thermodynamic analysis of the performance of the refrigerant fluid composition of the present invention, particularly with silicon dioxide nanoparticle additive, was performed in refrigeration and air conditioning systems using compressors and refrigerant fluids.

The influence of the new efficient coolant formulation with the related composition of the components, along with silicon dioxide nanoparticles with colloidal kinetic stability, on the performance of refrigeration and air conditioning systems was verified.

Temperature and cycling lowering tests were performed according to NBR12866 and NBR12869, respectively, in order to obtain the results of increased performance in refrigeration and air conditioning systems as a whole, with an expressive gain in the following operating parameters: - Cycle numbers / delta-t / per hour;

- suction and discharge pressures;

- Percentage of operating time of the equipment quantity of drive;

- Compressor crankcase temperature;

- Evaporation / insulation temperature;

- Condensation temperature;

- IYJ thermal conductivity in heat exchangers;

- Energy consumption up to temperature set-point;

- Total consumption of energy and power consumed;

- Lubrication, miscibility and viscosity of the lubricating oil with the refrigerant.

There was also an increase in the thermal conductivity with the reduction of the friction caused between the wall of the copper tubing and the refrigerant and the reduction of the friction in the wall of the compressor head, with an improvement in the lubrication characteristics and the viscosity of the oil due to the increase of the mass fraction of nanoparticles in the base coolant.

The composition of refrigerant fluid was miscible with all types of lubricating oils on the market, including mineral oil, synthetic polyester / POE / oil and alkybenzene oil.

Also, the thermodynamic performance gains were observed in the condensation temperature, with a gain of 25.9% in thermal efficiency compared to other conventional fluids.

Due to the low suction and discharge pressure characteristics, the refrigerant composition was considered safe for use as a direct substitute / drop-in7 for any existing common refrigerant market fluid, since the condition of manufacturing refrigeration equipment and air conditioning systems are prepared for nominal working conditions at higher pressures.It is usually guaranteed by equipment manufacturers using the common gases such as R22 / R1 34a / R407 / R404, a maximum pressure of up to 400psi, and for R41 0, a maximum pressure of up to 700psi. In all cases, they are much higher pressures than the pressures used by the novel refrigerant composition of the present invention, which does not exceed conditions of 60psi low and 240psi high. The relief of the cooling system as a whole, due to the gain of the parameters and thermal variables with the decrease of the friction, the significant increase of the thermal conductivity / K /, the decrease of the suction and discharge pressures, generate a significant increase of the useful life of the equipment where the new high-performance refrigerant formulation was implemented, especially with a nanoparticle additive, and its use in refrigeration and air conditioning systems is considered safer compared to common refrigerant fluids.

Example 1

The refrigerant composition of the present invention (difluoromethane, pentafluoroethane, tetrafluorethane, tetrafluoropropene and trifluoroethane) was tested against a known composition of the state of the art of chlorodifluoromethane-CHCIF2 (R 22 fluid) in a LG 12,000 Btu / h refrigeration equipment .

The data obtained are compiled in the tables below:

The graph of Figure 1 demonstrates the power decrease obtained with the refrigerant composition according to the present invention.

Example 2

The refrigerant composition of the present invention has been tested comparatively to a composition known in the art (R 22 fluid) in a Springer 9,000 Btu / h refrigeration equipment.

The data obtained are compiled in the tables below: Fluid Pressure R 22 Invention

Suction 65 PSI 45 PSI

Temperature Fluid R 22 Invention

Air Insulation 12 ~ 0 06.4 ^to C

Measurements of Fluid R 22 Invention

Chains

Fasel Phase2 Phase3 Fasel Phase2 Phase3

Voltage (V) 220 220 220 220

Current (A) 3.89 3.89 2.5 2.7

Power (W) 855.8 856 0 550 594 0

The graph of Figure 2 demonstrates the power decrease obtained with the refrigerant composition in accordance with the present invention.

Example 3

The refrigerant composition of the present invention has been tested comparatively to a composition known in the art (R 22 fluid) in a Midea 30,000 Btu refrigeration equipment.

The data obtained are compiled in the tables below:

Fluid Pressure R 22 Invention

Suction 50 PSI 50 PSI

Download 250 PSI 120 PSI

Temperature Fluid R 22 Invention

Air return 20.5 ^S C 19 ^S C

Air Insulation 7 ^S C 3.3 ^Q C

Suction temperature 13 ^and C 7 ^and C

Discharge temperature 19 ^S C 17 ^e C

Crankcase temperature 55 ^and C 33 "C

Ambient temperature 20 C ⁹ ^and C 19

Measurements of Fluid R 22 Invention

Chains Fasel Phase2 PHSG3 Fasel Phase3

Voltage (V) 220 220 220 220

Current (A) 1 0.8 1 1 7.5 7.7

Power (W) 2,376 2,420 1, 650 1, 694

The graph of Figure 3 demonstrates the power decrease obtained with the refrigerant composition according to the present invention.

Example 4

The refrigerant composition of the present invention has been tested comparatively to a composition known in the art (R 22 fluid) in a Split Carrier 9,000 Btu refrigeration equipment.

The data obtained are compiled in the tables below:

The graph of Figure 4 demonstrates the power decrease obtained with the refrigerant composition according to the present invention.

Example 5 The refrigerant composition of the present invention has been tested comparatively to a composition known in the art (R 22 fluid) in a Springer Carrier 90,000 Btu refrigeration equipment.

The data obtained are compiled in the tables below:

The graph of Figure 5 demonstrates the power decrease obtained with the refrigerant composition in accordance with the present invention.

Example 6

The refrigerant composition of the present invention has been tested comparatively to a composition known in the art (R 22 fluid) in a Springer Carrier 30 TR refrigeration equipment.

The data obtained are compiled in the tables below:

Fluid Pressure R 22 Invention

Suction 55 PSI 50 PSI

Download 265 PSI 1 35 PSI Temperature Fluid R 22 Invention

Air return 22.8 ³ C 22.5 ^S C

12.5 supply air ^to C 3.5 ^and C

Suction temperature 11 ° -5.5 ° C

Outlet temperature 31 ° C ^and 9 1 -C

Crankcase temperature 83 ^and C 54 ^S C

The graph of Figure 6 demonstrates the power decrease obtained with the refrigerant composition in accordance with the present invention.

Example 7

The refrigerant composition of the present invention has been tested comparatively to a composition known in the art (R 22 fluid) in a Hitachi 50,000 Btu refrigeration equipment.

The data obtained are compiled in the tables below:

Fluid Pressure R 22 Invention

Suction 60 PSI 50 PSI

Download 260 PSI 1 30 PSI

Temperature Fluid R 22 Invention

Air return 24 ^and C 21 ^to C

Air Insulation 14.5 ^Q C 3.4 ^Q C

Suction temperature 22 ^and C 7.3 ^and C

Discharge temperature 39 ^S C 18 ^and C

Crankcase temperature 68 ^and C 33 ^and C

Ambient temperature 22 ^and C19 ^and C Measurements of Fluid R 22 Invention

Chains

Fasel Phase2 Phase3 Fasel Phase2 Phase3

Voltage (V) 220 220 220 220 220 220

Current (A) 18.5 18.1 18.1 9.6 10.1 10.4

Power (W) 4,070 3,982 2.1 12 2,222 2,288

The graph of Figure 7 demonstrates the power decrease obtained with the refrigerant composition according to the present invention.

Example 8

The technology company IMG Energy and Sustainability also performed comparative tests between the refrigerant composition of the present invention, and a composition known from the prior art of tetrafluoroethane-C2H2F4 (R134 fluid).

The results of reduced consumption (60.8% reduction) and lower current (48.2% reduction) for the composition of the present invention are summarized in the graph of Figure 8.

Example 9

The refrigerant composition of the present invention has been tested in comparison to a prior art composition of a mixture of difluoromethane-CH 2 F 2 - and pentafluoroethane-CHF 2 CF 3 - (R 410A fluid) in two RT 10 machines each manufactured by Hitachi.

In one machine the refrigerant of the present invention was placed in place of the R410A and also installed the Global driver in the compressor for comparison of the electric power consumption of the two machines.

The results of lower inflation temperature (reduction of 0.7 ^to C) are summarized in the graph of Figure 9.

Further, there was a 42% reduction in consumption with fluid exchange (488 kWh with the R 41 0 A fluid and 285 kWh with the fluid of the present invention).

There is a gain through the lower inflation temperature using the refrigerant compositions of the present invention, rather than the compositions known in the art, in addition to pressure relief in almost all cases (mainly at low and suction pressures ).

As is well understood by those skilled in the art, it is possible numerous modifications and variations of the present invention in light of the teachings above without departing from its scope of protection as defined by the appended claims.

Claims

1 . A refrigerating fluid composition comprising the following components:

a) at least one difluoromethane;

b) at least one pentafluorethane;

c) at least one tetrafluoroethane;

d) at least one tetrafluoropropene; and

e) at least one trifluoroethane.

A composition according to claim 1, characterized in that the tetrafluoroethane is 1,1,1,2-tetrafluoroethane.

A composition according to any one of claims 1 to 2, characterized in that the tetrafluoropropene is 2,3,3,3-tetrafluoropropene.

A composition according to any one of claims 1 to 3, characterized in that the trifluoroethane is 1,1,1-trifluoroethane.

COMPOSITION according to any one of claims 1 to 4, characterized in that the components have the following proportions:

b) from 20 to 30% by weight. of pentafluoroethane, relative to the total weight of the composition;

d) from 15 to 25% by weight of tetrafluoropropene, relative to the total weight of the composition; and

A composition according to any one of claims 1 to 5, characterized in that it additionally comprises nanoparticles.

A composition according to claim 6, characterized in that the nanoparticles have a particle size ranging from 1 to 20 nm.

A composition according to any one of claims 6 to 7, characterized in that the nanoparticles are selected from of the group consisting of: graphite, silver, zinc and silicon dioxide, and mixtures thereof.

A composition according to any one of claims 6 to 8, characterized in that the nanoparticles are of silicon dioxide.

A composition according to any one of claims 6 to 9, characterized in that the amount of nanoparticles is up to 5% by weight, based on the total weight of the composition.

1 1. USE OF THE COMPOSITION, as defined in any one of claims 1 to 10, characterized in that it is in a refrigerator.

Refrigerating apparatus, characterized in that it comprises at least one heat exchanger, at least one compressor, and the refrigerant composition as defined in any one of claims 1 to 10.

PACKAGED PRODUCT, characterized in that it comprises an outer wrapper, storing the refrigerant composition as defined in any one of claims 1 to 10.

A method of packaging the refrigerant composition as defined in any one of claims 1 to 10, characterized in that it comprises the steps of:

b) weighing the composition; and

c) envaze of the composition.